Method for production of coumarone-indene type resins



Feb, l, `19441. E. 1 CLINE ETAL METHOD FOR PRODUCTION OFCOUMARONE-INDENE TYPE RESINS Filed July 12, 1941 FFII! @SSS vlNvrEN-ronsPatented Feb. l, 1944v METHOD Foa PRODUCTION OF cousinnoNE-INDENE 'rrraaasms Edwin L. Cline, Philadelphia, Pa., and David F.

Gould, Riverton, N. J., aslixnors, by mesne assignxnents, to AlliedChemical a Dye Corporation, a corporation of New York Application .my12, 1941, serial No. 402,142

Y -7 claims. (ci. 26o-s1) This invention relates to a process andapparatus for production of a coumarone-indene type resin by rapidcontinuous polymerization of a resin oil. l

In the polymerization of coumarone-indene crudes for the production ofresins it is consid-- ered of industrial advantage to carry out thepolymerization in a rapid continuous manner. In the means heretoforeprovided, however, for continuous polymerization, the resins producedhave not been of satisfactorily high quality.v The increasing use ofthese resins for the compounding of special coating materials andrelated prodther feature is the means by which the proportion ofeflluent returning to the polymerlzer is v controlled.

ucts of carefully controlled characteristics has made it increasinglyimportant that these resins should meet strict specications. Two of theimportant specifications imposed on these resins relate to melting pointand vegetable oil solubility. The resins heretofore produced bycontinuous polymerization have often'possessed an undesirably lowmelting point, and when an effort has been made to improve their meltingpoint, the resins produced by rapid continuous I polymerization methodshave been characterized by extremely poor solubility in vegetable oils.

It is an obj-ect of this invention to providea new method and apparatusfor carrying out rapid continuous polymerization of coumarone-indeneresin oils whereby resins of improved physical qualities, particularlyimproved solubility in vegetable oils, maybe obtained.4

We have discovered that high-quality couma- 'rone-inden'e type resins,and particularly resins of high solubility in vegetable Oils, areobtained in continuous catalytic polymerization of a coumarone-indeneresin oil when a controlled proportion of the polymerization reactionproduct is diverted and mixed with the unpolymerized oil and catlaystentering the polymerization reaction zone. We have further found. inaccordance with our invention, that the above-described improved resinproduct may be obtained by carrying out the polymerization in anapparatus comprising a polymerlzer where intimate contact 'between thecrude and the catalyst is established in a rapid continuous manner,provided with a branched 'outlet which includes a return duct fordiverting and returning a controlled proportionl of the eilluentreaction mixture back into -the polymerizer, the return duct havingmeans for introduction of fresh unpoiymerized oil and fresh catalystnear the point where recycled material is reintroduced into thepolymerizer. Another feature of our apparatus is the provision of acooling jacket surrounding the recycling duct, and a fur- In theaccompanying drawing,

Figure 1 is an elevation view of a preferred embodiment of ourinvention, illustrating, in nowdiagram form. a preferred process forcarrying out our invention, and including, in diagrammatic form, apreferred embodiment of the apparatus of our invention, and

Figure 2 is a Dian view of a part of Figure 1, illustrating in greaterdetail the recycling method and apparatus of Figure 1.

The process of our application is vapplicable for the production Aofcoumarone-indene type resins from coumaroneindene crudes in generalderived from the usual sources for this type of crude, i. e., coke-ovenoperations, water-gas operations and petroleum cracking and reformingoperations; particularly from coumarone-indene fractions boiling withinthe ge about to 205 C. obtained from such sources as coke-oven lightoil, drip oil, distillates from coke-ovenvtar, and particularly crudescontaining indene as the predomlnating polymerizable' component. Besinoils of thisV type generally contain such polyhomologs usuallypredominating. We have found it particularly advantageous to employ anoil containing less than 30% polymerizable material for thepolymerization process of our invention.

Such an oil may be obtained by the blending or dilution of a moreconcentratedV crude. for example. by addition to the crude of a reiinednaphtha containing little or no polymerizable material. In practicingthe process of our invention a coumarone-indene crude, for example, anaphtha of coke-oven or drip-oil origin, may first be subjected topurification treatments such as distillation or chemical treatments orboth, depending on the source and purity of the crude. v In carrying outthe polymerization process of our invention, the temperature of theresin olV feed may be as high as 40 C., but is preferably in the range25 to 5 C. We have found it particularly advantageous to .use aprecooled resinl oil as feed: l. e., to maintain the resin oil feedtemperature in the range 25 to 15 C.

Polymerization of resin-forming vconstituents in the oil is broughtabout by mixinga catalyst such as sulfuric acid or metallic halide withthe oil, and agitating the mixture to bring about intimate contact ofoil and catalyst, ifor example, y

' by forming a ne dispersion of sulfuric acid catalyst in the oil oreffectlner dissolution of stannic chloride catalyst in the oil. Thepreferred catalyst for use in our process is sulfuric acid. Thepreferred concentration of the sulfuric acid catalyst is in the rangeabout 78% to 100% sulfuric acid, particularly about 93% sulfuric acid(66 B), and 1% toy 2% of the acid, based on the volume of the oil, ispreferably employed.

In our preferred process the mixture of oil and catalyst is subjected tocontinuous polymerization, the polymerizer eiluent is divided into twostreams, one of which is withdrawn as polymerizer output, and freshunpolymerized oil and catalyst are continuously fed into the otherstream of polymerizer effluent, which is being returned to thepolymerizer. The volume ratio of 'recirculated material to unpolymerizedoil feed is preferably in the range 5:1 to 60:1, particularly 25:1 to50:1; this ratio may be maintained by suitably controlling the rate offeed I of catalyst and oil to the polymerization zone or l is finelydispersed, polymerization takes place rapidly throughout the body of oilat the greatly increased interface surfaces. The agitation of the oiland catalyst to bring about dissolution or dispersion is accomplished ina rapid and continuous manner by passing the mixture through suchapparatus as a colloid mill, a centrifugal pump, or other equipmentcapable of dispersing sulfuric acid in a resin oil. Polymerization ofresin-forming constituents of the oil feed, we have found, may thus bebrought about during the time of travel from the point of entrance ofoil feed into the polymerizer to the peint of division of polymerizereiuent into output and recycled material. We consider it preferable, in

the process or our invention, to ilmit this polymerization time to lessthan one minute, and preferably to less than ten seconds. in otherwords, the space velocity through the polymerization zone (i. e. thevolume rate of dow of material through the polymerizationv zone dividedby the volume of the polymerization zone) should preferably be greaterthan one reciprocal ute, and it is particularly advantageous to employ aspace velocity greater than sin reciprocal minutes. l

The portion oi the polymerized product not diverted for recycling istreated to separate catalyst, for eple by centrif settling, distillationor wg. uliuric acid catalyst, for example, lmay be separated bycentriiueing the portion of polymerizer effluent withdrawn as output, orby quenching in `eater and settling to separate the oil from the water.The separated oil is then washed with a caustic solution-for erramplesodiurn hydroxide solution, to neutralize residual acid, the causticwash solution is separated, and the polymerized oil treated for recoveryof the resin product in the usual manner, e. g., by distillation.

The process o! our invention makes possible the rapid, eillcientproduction oi ccarone-indene resins of surprisingly high quality; i. e.,light color, high-melting point and high solubility in vegetable oils.Our method and apparatus involving recycling of a portion of thepolymerized material is also advantageous in its flexibility withrespect to controlling the properties of the resin` product, e. g., themelting point andlsolubility ofthe resin; that is, the properties of theproduct by means of our recycling method' and apparatus may easily andquickly be controlled to a `desired value by simple regulation oftherecirculation ratio and rate of ow of materials. As indicated above,resins to be employed in various special coating compositions must meetstringent speeications. For example, resins which are to be blended withvarious vegetable materials must have a high vegetable oil solubilityandat the same time must have a satisfactory melting point; ourrecycling method and apparatus makes it possible, by simple regulationof recirculation ratio, to produce a resin of high vegetable oilsolubility without permitting the melting point of the resin to fall toan unsatisfactorly low value. Moreover, the recycling of a portion ofthe polymerized material permits closer controll of process variables;for example, polymerization temperature may be controlled by cooling therecycled material. Thus the comblnation of rapid continuouspolymerization and controlled recirculation, with all its attendantadvantages, provides a commercially attractive process for producingresinsof unusually favorable properties. Resins of particularly highqualitymay be produced when the resin oils are pre-cooled to lowtemperatures prior to polymerization.

In the drawing, reference numeral l indicates a polymerizer capable ofbringing about intimate contact between a resin oil, acid catalyst andrecycled oil in a rapid `and continuous manner. The polymerizer may, forexample, be a colloid mill or a centrifugal pump; a Charlotte colloidmill with clearance between rotor and stator set at .015 inch has beenfound advantageous; Reference numeral 2 indicates an unpolymerized oilstorage tank which may be provided with a cooling arrangement forpre-cooling the oil; 3 indicates a sulfuric acid catalyst storageRegulated amounts of the unpolymerized oil and fresh catalyst acid arefed into the recirculated material entering polymeriser i. Thepolymerization reaction product wdithdrawn at t is divided into the twostreams EB and Ei. The stream @i is the lportion of the polymerizationproduct recycled to the polymerizer. ie proportion of poerizationreaction product diverted through branch u is controlled by valve i;additional regulatory me (not shown), for controlling the dow ofmaterial, may be included in the conduit Si through which reactionproduct is withdrawn from the polymerizer system. The jacket 8, throughwhich cooling brine may be circulated, surrounds the branch passage t.The reaction product withdrawn from the system through pipe is ied tocentrifuge @where the spent acid is separated and discharged through l0.Instead of a centrifuge. a settling tank may be used for the separationof spent acid. The separated oil passes through duct ll to the mixingtank i2 of the neutralizer where it is treated with caustic solutionfrom the tank it. The oil and causticV solution are pumped bycentrifugal pump i4 into the tower l5, where the washing oi the oil withthe caustic solution is completed. The mixture of oil d wash solution ispassed through pipe I6 to tank I1 where the caustic solution isseparated through discharge pipe I8. The polymeiized oil thus obtainedmay be treated to recover the resin product. g v

The following 'examples are illustrative of the process of ourinvention:

Example 1.-A crude Hi-Flash naphtha iraction (boiling range 170 to'182C.) wie '70% of polymerizable materia-l was diluted with part-renedHi-Flash to form a mixture containing 26% of -polymerizable material.The mixture was pre-cooled to 27 C. The precooled resin oil was ied to apolymerization apparatus, consisting of a Charlotte colloid mill withclearance between rotor and stator set at .015 inch, at the rate of 0.9liter per minute; 66 B. (93%)y sulfuric acid was supplied at the rate of0.018 liter per minute. Therewas thus 2% of the 66 B. sulfuric acid,based on the volume oi' the oil, in the reaction mixture. The colloidmill was connected to a jacketed recycling tube provided with side armpipes for feeding the resin oil and sulfuric acid catalyst as shown onthe drawing. The control valve (shown as 7 on the drawing) was openedwide to give a'volume ratio of 54 to 1 for the rate of recycling to rateoi feed of fresh resin oil. Polymerized oil eluent withdrawn forrecovery oi resin had a. temperature' of 7 to 10 C. as it left thepolymerizer. This effluent was quenched continuously with water, set-.tied to separate water and spent acid, and the oil neutralized andworked up ior resin in the customary manner.

The resulting resin had a melting point ci 110 C. and a vegetable oilcloud point of 20 C. indicated by first appearance of a cloud when asolution of the resin in rapeseedoil was chilled in accordance with thestandard procedure for determining vegetable oil solubility, hereinafterdescribed.

Example 2.-'-The same oil asin Example l vwas treated by the proceduredescribed in that enample, except that the oil was pre-cooled to atemmrature of C. instead oi' 27 C. '111e temperature oi the eiiluentleaving the polymerizer in this case was 9 to 12 C.

The resin recovered from the reaction product had a melting point of 138C.. and a solution of the resin in rapeseed oii when tested according tothe standard procedure showed a rst cloud at C.

Esempio 3.--The procedure oi Example 1 was carried out except that therateoi feed oi. fresh oil and catalyst was doubled, i. e., increased to1.8 liters per minute for the iresh oil and 0.636 liter per minuteiorthe acid catalyst. The volume ratio oi recycled4 oilto fresh oil wasthus 27 to 1. instead of 51 to 1. The eiuent leaving the polymerizer hada 'temperature oi 5 to 13 C.

The resin recovered from this reaction product had a melting point oi145 C. and a cloud point in rapeseed oil of 10 C.

Example 1 -A resin .oil as in Example 1 was maintained'at 30 C., fed tothe polymerizer at a rate of 3.6 liters per minute. and sumcient 100%sulfuric acid 4was i'ed to maintain the proportion of catalyst at 2% oi100% acid based on the volurne oi' the oil. The volume ratio oi'recycled oil to fresh oil was 13 to 1. The oil emuent from the Ipolymerizer had a temperature 011 to 2 C.

The resin recovered from this reaction product had a melting point ci123 C., a good vegetable' oil solubility, and a color of C-l V4.

li'ammple 5.-A resin oil as in Example 1 oon'- taimng 26% poiymerizableswas fed to. the polylill table oil solubility, and a color merizerA atthe rate of 6 liters per minute. 160% suliluric acid was red at acorresponding rateso' as to maintain a proportion of 2%.catalyst basedon the volume of the oil. The volume ratio of recycled oil to fresh oilin this run was 7 to l. The

oil feed had a temperature of 30 C. and the ei'iluent from thepolymerizer had a temperature of 3 to 4 C.

The resin recovered from this reaction mixture had a melting point of120 C., a good vegcoi C-lle. Thus it is seen that e'vcn with a recyclingratio as low as 7, a resin of high quality,l is produced.

Example 6.-A resin oil andsuliuric acid were fed to a polymerizer as inExample l and the recycling valve was set to give a volume ratio ofrecycledoil to fresh oil ofi 8 to l. The oil feed w'as pre-cooled toatemperature of 15 C. and the eiliuent from the polymerizer was ture of 6to 12 C.

y The resin recovered from had a melting point of 153 C. and the cloudpoint oi' a rapeseed oil solution was 32 C. 1t is noted the vegetableoil solubility of this product, though satisfactory, was somewhat lowerthan in previous runs, due to the fact that a relatively low recyclingratio was used in this run. The melting point of the resin product,vhowever, was very satisfactory and the vegetable oil solubility was muchbetter than would have been the case without recycling.

For purposes of lcomparison with Examples-1, 2, 3 and 6, involvingpre-cooling oi the resin oil and use oi 66 Be. acid, a run-was made withthe recycling valve closed so that the ratio of rethis reaction mixture.cycled oil to fresh oil was zero. A resin oil as in Example 1,containirnrr 26% polymerizables. was pre-cooled to 20 C., led to thepolymerizer, without recycling, at a rete of 3.6.liters per minuta, andsufilcient 66v B. acid was added to maintain the proportion of catalystat 11/2% based on the volume or the oil. The. resin recovered in thiscase had a rapeseecl oil cloud point oi '72 C., and e. melting .point oi171 C.

lt is noted from the above comparison that when the volume ratio of.recycled oil to fresh oil is high, as in Examples 1, 2 and 3, the resinprocluct has an unusual combination of properties, namely adequatelyhigh melting point and extremely good solubility in vegetable oils. 1t4is further noted that even when of recycled oil to fresh oil Example 6,the vegetable oil solubility is still nood, i. e., a rapeseed cloud oi32 C. as compared to '72 C. when no recycling is employed. and the isrelatively low, as in melting point is quite satisfactory.

The resin recovered from this reaction mixture had a melting point or118 C. and a solution oi the resin in rapeseed oil showeda slight cloudat 20 C. v

Example 8.-'Ihe following run was made using a resin oilhaving apolymeriz'able content outside the preferred range. A resin oilblended-as described in Example 1 so as to bring the concentration oipolymerizables to 36% was fed to at a temperathe volume ratiotemperature oi the ieed oil the poiymerizer at the rate of 1.2 litersper minute and 66 B. sulfuric acid was fed at such a rate as to maintainthe proportion of catalystqat 2% based on the volume of the oil. Therecycling 1 -atie was maintained at 40. The temperature.

of the oil feed was 30 C. and the temperature of the eilluent from thepolymerizer was 4 to 19 C. The resin recovered from this reactionproduct had a melting point of 107 C., good solubility in vegetable oil,and a color of C-1/2|. In spite of the high polymerizable content andhigh temperature of the resin oil satisfactory quality for many purposeswas obtained because the polymerization reaction mixture was recycled inaccordance with our invention.

'I'he standard test for vegetable oil solubility referred to above iscarried out as follows: 17.7 grams of resin and 18.2 grams of rapeseedoil are heated and held at a temperature of 140 to 150 C. until a clearsolution is obtained. This solution is poured into a 20 x 175 mm. testtube to a depth of 6 cm. The solution is cooled to room temperature, thetime noted, and after standing for onehour atroom temperature thepresence or absence of cloudiness in the solution is noted.

If the solution remainsclear, it is thereupon cooled to +l C., kept atthis temperature for one hour and again examined for cloudiness. Thisprocedure is repeated for the temperatures 0 C., 10 C. and 20 C.successively. The test is carried through in continuous fashion withoutdelay or deviation from the specified periods of time.

The color of the resin according to the standard resin color scalereferred to above is determined as follows: The resin scale isdetermined by mixing three stock solutions in the proportions indicatedin the following table, thereby obtaining the colors indicated in thistable; namely, stock solution A constituted of 40 cc. of 33.5%Ihydrochloric acid and 1560 cc. of water; stock solution B made bytriturating 450 grams of C. P. ferric chloride (FeClaHzO), 270 cc. ofsolution A and filtering, using the clear filtrate for stock solution B;and stock solution C made by triturating 60 grams of C. P. cobaltchloride (CoClzHzo) and 60 cc. of solution A and ill.- tering, using thefiltrate for stock solution 0.

Volumes in. cubic centimeters A B 0" Water Standard C series feed, aresin product of til the depth of the color of the resin solution thusproduced is compared with the standard colors. If the sample liesbetween two consecutive numbers, its color is reported as the higherone.

Since certain changes in carrying out the above process and in theconstruction -set forth, which embody the invention, may be made withoutdeparting from its scope, matter contained inI the above description orshown in the accompanying drawing shall be interpreted as illustrativeand not in a limiting sense. v

What is claimed is:

1. In a process for the production of high quality coumarone-indene typeresins by continuous catalytic polymerization ofa coumarone-indene resinoil, the step which comprises recycling a controlled proportion of thepolymerization reaction product back to the polymerization reactionzone.

' 2. In a processfor the production of high quality coumarone-indenetype resins, the steps which comprise subjecting a coumarone-indeneresin oii to continuously catalytic polymerization, continuouslywithdrawing polymerization reaction product from the polymerizationreaction zone, diverting a controlled proportion of the withdrawnproduct, and continuously mixing the diverted material with the enteringunpolymerized resin oil.

3. In a process for the production of high quality coumarone-indene typeresins by rapid continuous catalytic polymerization of a coumaroneindene-resin oil, the steps which comprise diverting such a proportion of thepolymerization reaction' product for return to the polymerizationreaction zone that the volume ratio of recycled oil to enteringunpolymerized oil is in the range 5:1 to 60:1, and mixing the divertedoil with the entering unpolymerized oil and entering fresh catalyst.

4. In a process for the production of high quality coumarone-indene typeresins by rapid continuous catalytic polymerization of a coumaroneindeneresin oil containing less than 30% of polymerizable constituents, thesteps which comprise diverting such ay proportion of the polymerizationreaction product for return to the polymerization reaction zone that thevolume ratio of recycled oil to entering unpolymerized oil is in therange 25:1 to 50:1, mixing the diverted oil with the enteringunpolymerized oil, thereafter mixing entering sulfuric acid catalystwith the oil mixture, and passing the resulting mixture into and throughthe polymerization reaction zone at aspace velocity greater than onereciprocal minute.

5. In a process for the production of high quality coumarone-indene typeresins, the steps which comprise subjecting a coumarone-indene resin oilto rapid continuous catalytic polymerization, diverting a controlledproportion of the polymerization reaction product, and mixing it with'entering unpolymerized resin oil maintained at a temperature in therange 25 to 5 C.

6. A process for the production of coumaroneindene type resins whichcomprises continuously feeding a coumarone-indene resin oil at a.temperature not higher than about 40 C. to a polymerization reactionzone, continuously feeding about 1% to 2%, based on the volume of theresin oil, of about 78% to 100% sulfuric acid to` said reaction zone,continuously passing the resin oil and the sulfuric acid through apolymerization reaction zone at a'space velocity greater than it isintended that alione reciprocal minute to disperse the acid in the oiland bring about polymerization of polymerizable constituents of the oil,continuously witl'l-V drawing the polymerization reaction A`product fromthe reaction zone, dividing-the reaction product into two portions,continuously returning one of these portions to the polymerizationreaction zone at a rate such that the volume ratio of recycled oil toentering unpolymerized oil is in the range 5:1 to 60:1, and continuouslytreating the otherl said reaction zone, continuously passing the resinoil and the sulfuric acid through a polarization reaction zone at aspace velocity greater than six reciprocal minutes to disperse the acidin the oil and bring about polymerization of polymerizable constituentsof the oil, continuously withdrawing the polymerization 'reactionproduct from the reaction zone, dividing the reaction v product intotwo' portions, continuously cooling one of these portions and returningit to the polymerization reaction zone at a rate suchy that the volumeratio of recycled oil to entering unpolymerized oil is in therange 25:1to 50:1, and

continuously treating the other portion of they withdrawn reactionmixture to separate` acid therefrom, neutralize the oil and recover a.resin product. A

.EDWIN L.V CLINE.

DAVID F. GOUID

